Polymerization catalyst and method

ABSTRACT

An olefin polymerization and copolymerization catalyst active in the presence of an alkyl aluminum cocatalyst is prepared by mixing, in the presence of a solvent, particles of a silica or alumina material having reactive surface groups, and a magnesium alkyl or a magnesium alkyl-aluminum alkyl complex of the general formula (MgR 2 ) m  (AlR 3  &#39;) n  where R and R&#39; are alkyl groups and m/n is between about 0.5 and 10, inclusive, to form a hydrocarbon insoluble reaction product which is then mixed, in the presence of a solvent, with an electron-donating alcohol and a titanium, vanadium or zirconium halide, oxyhalide or alkoxyhalide, followed by removal, such as by evaporation, of the solvent to give a dry, granular, solid catalyst.

BACKGROUND OF THE INVENTION

The titanium containing catalyst of this invention is highly active andis suitable for polymerization of ethylene and other 1-olefins,particularly of 2-8 carbon atoms, and copolymerization of these with1-olefins of 2-20 carbon atoms, such as propylene, butene and hexene,for example, to form copolymers of low- and medium-densities. It isequally well suited for particle form, gas phase and solutionpolymerization processes, and is especially effective in the selectiveproduction of high-density polyethylene having a narrow molecular weightdistribution and high melt index for injection molding applications.

The catalyst of this invention has an enhanced sensitivity to molecularweight control by hydrogen. This makes it possible to make high meltindex particle form polyethylene with less hydrogen and at a lowerpolymerization temperature. The catalyst is also well suited for theproduction of high-strength fibers or film having a low melt index.

The catalyst does not require an excess of titanium and thereforeobviates the need for removal of catalyst residues from product polymer.The catalyst is suitable for use in particle form polymerization plantsdesigned for prior silica-supported chromium oxide catalysts.Heretofore, titanium catalysts have not been extensively used in suchplants due to the substantial excess of corrosive titanium compoundstypically used in the preparation of such catalysts. The presentcatalyst is easily injected into particle form reactors by means of wellknown automatic feeding valves, and corrosion-resistant materials ofconstruction are not required.

The most pertinent prior art known to me is as follows:

South Africa Appl. No. 69/3534, 10/5/69 by Van Den Berg and Tomiers ofStamicarbon describes catalysts made from organomagnesium compounds,alkyl aluminum chloride compounds, and titanium compounds which areincreased in reactivity by the addition of alcohols. A support, orgranular ingredient, is not used, there is no separation of the solvent,and the use of a cocatalyst is not part of the disclosure.

German Off. No. 2,721,058, Nov. 23, 1978 by Gunter Schweier et al. ofBASF reveals a catalyst with a porous inorganic oxide like silica orsilica-alumina as a support. A solution of a reaction mixture of analcohol, a titanium trihalide, and a magnesium compound is added to theoxide, and then the solvent (i.e. the alcohol) is evaporated giving anintermediate solid product. This solid product is suspended in asolution of organometallic compound, which may be an alkyl aluminum orsilicon halide compound. The suspended solid component may be used as isalong with an organometallic compound as a cocatalyst. The suspendedsolid compound can also be filtered, and washed prior to use, and forgas phase polymerization it can be coated with wax. The magnesiumcompounds are not alkyl magnesium compounds but alkoxides and halidesand other types of compounds. Another Schweier patent, German Off. No.2,721,094 is similar to this one. It reveals that the silica orsilica-alumina may be treated with an alkyl aluminum halide compoundbeforehand. U.S. Pat. No. 4,110,523, Aug. 29, 1978, also by Schweier etal. covers a similar catalyst. In this case, the treatment with thealkyl aluminum or silicon halide solution is eliminated.

U.S. Pat. No. 4,130,699, Dec. 19, 1978 by G. R. Hoff and Peter Fotis ofStandard Oil discloses a supported catalyst for vapor phasepolymerization which are made less active prior to feeding to thereaction vessel by treatment with alcohols, acetates, ketones,aldehydes, or esters.

U.S. Pat. No. 4,105,585, Aug. 8, 1978 by Ian Matheson of BP Chemicalsdescribes a catalyst prepared from the reaction of magnesium powder, atitanium halide and alcohol.

U.S. Pat. No. 3,647,772 by N. Kashiwa (Mitsui Petrochemical, May 7,1972) involves treating anhydrous magnesium carbonate with polar organiccompounds including alcohols. When this is done, more titanium fromtitanium tetrachloride can be fixed upon the magnesium carbonate.Catalyst reactivity, melt index and bulk density of the product areincreased by the treatment with the polar organic compound.

SUMMARY OF THE INVENTION

The catalysts of this invention give particle form polyethylene ofincreased bulk density and more uniform particle size distribution thanthe catalysts of the above South Africa 69/3534. In addition, there is adecreased degree of reactor fouling. These improvements are retained inthe catalysts of this invention which have the additional improvement ofan increased hydrogen sensitivity.

The improved catalyst of the invention is prepared by combining, in thepresence of a solvent, an alcohol and a magnesium alkyl or amagnesium-aluminum complex of the general formula (MgR₂)_(m) (AlR₃')_(n) with preactivated particles of an inorganic oxide material havingreactive groups. These reactive groups may be hydroxyls and/or oxidelinkages or similar surface groups. The reaction product therebyproduced is then reacted, in the presence of a solvent, with ahalogen-containing transition metal compound to form a supportedcatalyst component, followed by evaporation of the solvent. The catalystcomponent prepared according to the foregoing is active in the presenceof an effective quantity of an alkyl aluminum cocatalyst, preferablycomprising a trialkyl aluminum compound.

In this invention:

(1) The alcohol is either added to the solid inorganic oxide prior tothe introduction of the organomagnesium compound or the alcohol is addedto the mixture after the organomagnesium compound.

(2) The molar ratio of the alcohol to the organomagnesium compound isfrom 0.1 to 10.

(3) The alcohol contains only carbon, hydrogen, and oxygen, and does nothave an aromatic ring bonded directly to the alcohol hydroxyl group.

(4) The catalyst preparation reaction is conducted at temperatures fromabout 15° C. to about 100° C. with room temperatures being completelysatisfactory.

(5) Solvents added during the preparation are removed to yield afree-flowing catalyst.

The inorganic oxide material is chosen from the group consisting ofsilica, alumina and silica-alumina. The inorganic oxide material isutilized in finely divided form and is preactivated by heating in aninert atmosphere at temperatures of up to about 900° C.

The magnesium-aluminum complex is of the general formula (MgR₂)_(m)(AlR₃ ')_(n) where R and R' are alkyl groups and m/n is between about0.5 and 10, inclusive. R and R' may be the same or different alkylgroups of one to about 12 carbon atoms.

Magnesium alkyls are of this general formula MgR₂ when R is an alkylgroup of one to about 12 carbon atoms.

The optimum amount of organomagnesium compound depends upon the surfacearea of the reactive oxide and the concentration of polar groups on thereactive oxide surface. For highest reactivity, the molar ratio of theorganomagnesium compound to the polar groups should be at least one.

The transition metal compound is of the general formula Tr(OR)_(a)X_(4-a) or TrOX₃ wherein Tr is a transition metal selected from thegroup consisting of titanium, vanadium and zirconium, R is an alkylgroup of one to about 20 carbon atoms, X is a halogen atom and a is zeroor an integer of one to 4. Titanium compounds are preferred for highestreactivity.

The transition metal compound is reacted with the reaction product ofthe magnesium compound and the inorganic material, preferably inequimolar ratio, so that the resultant solid catalyst componentincorporates substantially all of the titanium in a highly active form.It is therefore unnecessary to remove nonreactive titanium from thecatalyst or from product polymer, as opposed to prior titanium catalystswhich usually require excessive titanium during preparation.

Modification of the catalysts by alcohols has a tendency to decreasetheir reactivity. In some cases, the titanium weight percent in thecatalyst can be increased in order to offset this tendency. For example,catalysts can be made by reacting dry Davison grade 952 silica withfirst a magnesium compound and then titanium tetrachloride. According tothis invention, such a catalyst can be modified by the addition of, forexample, N-butyl alcohol to the reaction product of the silica and themagnesium alkyl compound. In this case, it is desirable to increase thetitanium content when larger amounts of alcohol are used. The followingratios and combinations are preferred in this invention:

    ______________________________________                                        n-Butyl Alcohol/                                                                              TiCl.sub.4 mmols/g                                            R.sub.2 Mg      of 952 silica                                                 ______________________________________                                        0.25            1.25                                                          0.50            2.25                                                          1.00            2.25                                                          2.00            2.50                                                          ______________________________________                                    

The ratios of alcohol to magnesium can be selected on the basis of themelt index desired. Normally, the Mg/Ti is about 1.0. Hence, as alcoholand TiCl₄ are increased with respect to the dry silica, the amount oforganomagnesium compound must also be increased to remain in thepreferred relation.

Due to the catalyst's high activity, a relatively high partial pressureof hydrogen may be used in order to result in a high product melt index.Also, the catalyst's high activity makes feasible copolymerization ofolefins less reactive than ethylene.

The catalyst is, because of its high activity, equally well suited foruse in the particle form polymerization process in which the solidcatalyst component, the cocatalyst, and olefin monomer are contacted ina suitable solvent, such as the solvent used in the catalyst formingreaction, or in a gas phase process in which no solvent is necessary.

DESCRIPTION OF THE PREFERRED EMBODIMENTS I. Preparation of the InorganicOxide Material

The reaction product catalyst of the invention is formed and is bondedto the surface of the inorganic oxide materials by reaction with activesurface hydroxyl or oxide groups thereof. Polymerization reactionefficiency is dependent, to some extent, upon the physicalcharacteristics, such as surface area, of the inorganic oxide material.Therefore, it is preferred to utilize the inorganic oxide material infinely divided form. The amount of titanium compound is determined withrespect to the amount of magnesium compound within limits.

Suitable inorganic oxide materials include silica, alumina andsilica-alumina, with silica being preferred. The inorganic oxide maycontain small amounts of materials such as magnesia, titania, zirconiaand thoria, among others.

It is necessary to dry and preactivate the inorganic oxide material byheating in an inert atmosphere at an elevated temperature before contactwith the magnesium compound. In the case of Davison Chemical CompanyGrade 952 silica, optimum catalyst reactivities are obtained at anactivation temperature of about 600° C. in a nitrogen atmosphere,although satisfactory results are obtained at temperatures between about200° C. and 900° C.

II. Catalyst-Forming Reactants 1. The Organomagnesium Compound

Particles of the dried and preactivated inorganic oxide material areinitially reacted with an organomagnesium compound (MgR₂), ororganomagnesium-aluminum complex of the general formula (MgR₂)_(m) (AlR₃')_(n) in which R and R' are the same or different alkyl groups and theratio m/n is within the range of about 0.5 to about 10, and preferablybetween about 2 and 10.

The alkyl groups R may be the same or different, and each has between 2and 12 carbon atoms. When the R groups are identical, it is preferredthat each has at least 4 carbon atoms, and are preferably butyl or hexylgroups. The alkyl groups R' are preferably ethyl groups.

The reaction between the magnesium alkyl compound and the inorganicoxide particles is carried out in a solvent, preferably at roomtemperature for convenience. The catalyst-forming reactions may becarried out at higher or lower temperatures, if desired. The alcohol isadded to the inorganic oxide before or after the reaction with themagnesium alkyl compound.

The amount of the magnesium is chosen such that the total number ofmoles of magnesium is between about 0.1 to 10 times the number of molesof transition metal, the amount of which is chosen with reference to theweight of inorganic oxide, as is described below. It is preferred thatmagnesium be present in equimolar ratio to the transition metalcompound.

The magnesium-aluminum complex is known in the art as disclosed inAishima et al., U.S. Pat. No. 4,004,071 (Jan. 18, 1977) at col. 2, 11.34-40 and col. 3, 11. 30-36. The complex is readily prepared accordingto the teachings of Zeigler et al., "Organometallic Compounds XXII:Organomagnesium-Aluminum Complex Compounds". Annalen der Chemie, Vol.604, pages 93-97 (1957).

2. Alcohol

The alcohol may be added to the reactive oxide prior to the reactionwith the magnesium alkyl or magnesium-aluminum complex. If this is done,then the magnesium alkyl solution must be added within a short time sothat the previously added alcohol does not evaporate due to the flow ofinert gas through the preparation vessel. The alcohol may also be addedafter the magnesium compound.

The alcohol contains only carbon, hydrogen, and oxygen atoms, and doesnot have an aromatic ring bonded directly to the alcohol hydroxyl group.Because of cost and convenience, ethyl, propyl and butyl alcohols arepreferred. Primary, secondary and tertiary alcohols are effective, butn-butyl alcohol is preferred.

The molar ratio of the alcohol to the organomagnesium compound may befrom 0.1 to 10, but the greatest effect upon melt index and hydrogensensitivity is in the range of 0.5 to 2.0. Consequently, the preferredmolar ratio of alcohol to magnesium compound is between 0.5 and 2.0. Thetransition metal content of the catalyst may be increased at higheralcohol ratios to maintain high reactivity.

3. Transition Metal Compound

After the inorganic oxide particles are completely reacted with theorganomagnesium compound and alcohol, a selected halogen-containingtransition metal compound is reacted with the resulting hydrocarboninsoluble reaction product to form an active solid catalyst component.The catalyst-forming reaction is carried out in a solvent, preferably ahydrocarbon, and preferably at room temperature.

The transition metal compound is selected from those of the generalformula Tr(OR)_(a) X_(4-a) or TrOX₃ wherein Tr is titanium, vanadium, orzirconium, R is an alkyl group of one to about 20 carbon atoms, X is ahalogen atom and a is zero or an integer of one to 4. Suitabletransition metal halides include TiCl₄, Ti(OR)Cl₃, Ti(OR)₂ Cl₂, Ti(OR)₃Cl, VOCl₃, VCL₄, ZrCl₄, and others commonly used in conventional Zieglercatalysts, with R being as defined above.

For optimum reactivity, the transition metal is added to the inorganicoxide-magnesium compound-alcohol reaction product in equimolar ratio tothe total magnesium.

The ratio of transition metal compound with respect to the inorganicoxide material may vary over a relatively wide range, although it hasbeen found that the best results are obtained with a transition metalcontent of between about 0.25 and 1.0 mmoles per mmole of active surfacehydroxyl and oxide groups on the inorganic oxide material. Preferably,between 0.6 and 2.5 mmoles of transition metal compound should be addedto the reaction mixture per gram of inorganic oxide material.

III. Solvent Evaporation

After formation of the solid catalyst component by reaction of thetransition metal compound with the inorganic oxide-magnesium compoundreaction product, the solvent present in the catalyst-forming reactionmust be removed under an inert atmosphere. For example, evaporation mayoccur at a temperature between about 90° C. and 100° C. under a nitrogenatmosphere for from about 1/2 to 10 hours, or until dry. Solventevaporation is preferred to insure that product polymer is formed insmall particles suitable for a particle form process rather than insheets, fibers or chunks which rapidly foul the reactor and decreasereaction efficiency.

After solvent evaporation, the catalyst may advantageously be added to asolvent for reaction therein, as in the particle form polymerizationprocess. The solvent added to the catalyst may be the same solvent usedin the catalyst forming reaction, if desired, or may be any othersuitable solvent. The catalyst exhibits no loss in activity due toaddition to solvent.

Further, it has been found that although solvent evaporation is mosttypically carried out at an elevated temperature, it is evaporation andnot heating which ensures desirable product characteristics. Evaporationmay be carried out, if desired, at reduced pressure and temperature.

IV. Cocatalyst

The catalyst prepared as described above is active in the presence of analkyl aluminum cocatalyst. Trialkyl aluminum compounds such astriisobutyl aluminum (TIBAL) are preferred cocatalysts. The alkylaluminum compound is fed to the polymerization reaction zone separatelyfrom the solid catalyst component.

The proportion of cocatalyst to solid catalyst component may be varied,depending on the transition metal concentration in the solid catalystcomponent. In the case of TIBAL, excellent results have been obtainedwith as low as 4.6 mmole cocatalyst per gram of solid catalystcomponent.

V. Reaction Conditions

The particle form reaction system is characterized by the introductionof monomer to an agitated catalyst-solvent slurry. The solvent,typically isobutane, may be the solvent in which the catalystpreparation reaction is carried out. This type of reaction is bestcarried out in a closed vessel to facilitate pressure and temperatureregulation. Pressure may be regulated by the addition of nitrogen and/orhydrogen to the vessel. Addition of the latter is useful for regulationof the molecular weight distribution and average molecular weight ofproduct polymer, as is well known in the art. In this invention, theeffect is enhanced by the incorporation of an alcohol into the catalyst.

Particle form polymerization of ethylene with the catalyst of thisinvention is best carried out at about 80° C. to 110° C. at a pressureof between 35 and 40 atmospheres. In gas phase polymerization, thetemperature may range from less than about 85° C. to about 100° C. witha pressure as low as about 20 atmospheres. Copolymers may be produced byeither process by addition of propylene, butene-1, hexene-1 and similaralpha-olefins to the reactor. Production of copolymers of relatively lowdensity is preferably carried out at a relatively low temperature suchas 60° C. to 80° C.

EXAMPLES 1-14

A series of catalysts was prepared according to the invention modifiedby the addition of an alcohol. The alcohol was added to the granularingredient which in this case was Davison Chemical Company Grade 952silica previously dried at about 600° C. The catalysts were tested, withthe conditions and results given in the following Table, by adding thealcohol

                                      TABLE                                       __________________________________________________________________________    Example         TiCl.sub.4        H.sub.2                                     No.  ALCOHOL    mmol/g SiO.sub.2                                                                     ROH/Mg                                                                              Temp °F.                                                                    (psig)                                                                            Reactivity                                                                          MI                                __________________________________________________________________________    1    n-Butyl Alcohol                                                                          2.75   0.54  221  50  3199  1.44                              2    n-Butyl Alcohol                                                                          2.75   0.54  221  100 1292  24.7                              3    sec-Butyl Alcohol                                                                        2.25   0.50  215  50  3291  1.54                              4    sec-Butyl Alcohol                                                                        2.25   0.50  215  100 3766  5.80                              5    t-Butyl Alcohol                                                                          2.25   0.50  221  50  4196  0.95                              6    t-Butyl Alcohol                                                                          2.25   0.50  221  100 2494  8.13                              7    t-Butyl Alcohol                                                                          2.25   0.50  215  50  1214  2.28                              8    t-Butyl Alcohol                                                                          2.25   0.50  215  100  933  11.1                              9    cyclohexyl Alcohol                                                                       2.25   0.50  215  50  3600  1.87                              10   cyclohexyl Alcohol                                                                       2.25   0.50  215  100 1100  10.9                              11   benzyl Alcohol                                                                           2.25   0.50  215  50  2199  1.78                              12   benzyl Alcohol                                                                           2.25   0.50  215  100 1555  10.6                              13   None (Comparative)                                                                       2.25   --    215  50  5583  0.58                              14   None (Comparative)                                                                       2.25   --    215  100 5354  2.92                              __________________________________________________________________________     In each case, the molar ratio of TiCl.sub.4 to R.sub.2 Mg was 1.0.            All parts and percentages herein are by weight.                          

A quantity of dried silica was mixed under nitrogen with the alcohol,then dibutyl magnesium-triethyl aluminum complex in heptane solution wasadded. The combination was stirred for 30 minutes at ambient temperaturebefore adding titanium tetrachloride. After the addition of the titaniumtetrachloride, the reaction mixture was stirred for another 30 minutes.The flask was then immersed in an oil bath at a temperature of 90° C.for a period of 30 to 60 minutes, to give a dry, granular catalyst. Fromthe Table it can be seen that the alcohol modification results in anincrease in melt index with respect to the control experiments.

The following examples illustrate that the order of adding the magnesiumcompound and the alcohol may be reversed without affecting the alcohol'sincreasing the MI (melt index).

EXAMPLE 15

A catalyst was prepared using heated Davison grade 952 silica asdescribed in Example 1, but the order of adding the ingredients waschanged. In this case, 2.3 g of the silica was combined with 23 ml dryhexane and 9.7 ml of dibutyl magnesium-triethylaluminum complexsolution. This volume of solution gave 1.75 millimoles of dibutylmagnesium per gram of silica. The combination was stirred at roomtemperature for thirty minutes under a flow of nitrogen, then 0.38 ml ofn-butyl alcohol was added. The calculated molar ratio of dibutylmagnesium to n-butyl alcohol was 1.0. The reaction mixture containingthe alcohol was then stirred for another thirty minutes before 0.44 mlof titanium tetrachloride was added. The Mg/Ti atomic ratio was 1.0.After another thirty minutes reaction time, the flask was immersed in anoil bath at a temperature of 98° C. The flask was kept in the hot oilbath until the catalyst was free of solvent. The evaporation was aidedby a flow of nitrogen through the flask which was maintainedcontinuously.

A portion of the dry catalyst was tested for making a low densityethylene-butene-1 copolymer. As in previous examples,triisobutylaluminum was the cocatalyst. The amount oftriisobutylaluminum was 9.2 millimoles per gram of catalyst. Catalystand cocatalyst solution were mixed with 500 ml isobutane at 160° F. in a1400 ml polymerization vessel. Hydrogen was added to give a 50 psiincrease in pressure, then ethylene and butene-1 were introducedsimultaneously. The amounts were selected to give 22 wt.% butene at atotal pressure of 350 psig. Ethylene was then fed as required to keepthe pressure constant at 350 psig. Butene-1 was pumped into thepolymerization vessel at a constant rate of 15 g/hr.

At the end of the polymerization test, the polymer product was found tohave a density of 0.917 g/cm³ and a melt index of 3. The reactivity was5500 g/g cat/hr. Since similar catalysts without the addition of alcoholgive low density copolymer with a melt index of about 1.0 under theseconditions, this example shows that the alcohol can be added after themagnesium compound and result in an increase in melt index.

EXAMPLE 16

The catalyst of Example 15 was also tested in ethylenehomopolymerization. The conditions of polymerization were the same as inExample 4, that is 215° F. with 100 psi of added hydrogen. However, areactor of larger capacity was employed so that the 100 psi correspondsto a larger quantity of hydrogen. The results of two tests under theseconditions (Tests A and B) were as follows:

    ______________________________________                                                       Test A                                                                              Test B                                                   ______________________________________                                        TiCl.sub.4                                                                    mmol/g SiO.sub.2 1.75    1.75                                                 ROH/Mg           1.0     1.0                                                  Temp °F.  215     215                                                  psi H.sub.2      100     100                                                  Reactivity       911     900                                                  Melt Index       48      47                                                   ______________________________________                                    

A similar catalyst without alcohol in this larger reactor vessel yieldsas ethylene polymer with a melt index of about 10. Therefore, thisexample again shows that the alcohol can be added after the magnesiumcompound and will produce an increased melt index.

I claim:
 1. A dry, granular and solid olefin polymerization andcopolymerization catalyst active in a particle form process in thepresence of an organic cocatalyst prepared by reacting, in the presenceof a solvent, reactive materials comprising dry particles or aninorganic oxide having active surface hydroxyl or oxide groups andchosen from the group consisting of silica, alumina and silica-alumina,said particles having been preactivated by heating at between about 200°C. and 900° C., and an alcohol containing only carbon, hydrogen andoxygen atoms and no aromatic ring bonded directly to the alcoholhydroxyl grup and an organomagnesium compound comprising a magnesiumalkyl or a complex of the general formula (MgR₂)_(m) (AlR₃ ')_(n) whereR and R' are the same or different alkyl groups of 2-10 carbon atomseach and m/n is between about 0.5 and 10, inclusive, to form a reactionmixture of said solvent and a hydrocarbon insoluble first reactionproduct, the molar ratio of said alcohol to said organomagnesiumcompound being 0.1-10 mixing said reaction mixture with a halide,oxyhalide or alkoxyhalide of a metal chosen from the group consisting oftitanium, vanadium and zirconium to form a second reaction product, andremoving the solvent from said second reaction product to form said dry,granular and solid catalyst.
 2. The catalyst of claim 1 wherein saidcompound is a magnesium alkyl of the formula MgR₂ where R is an alkylgroup of 2 to 10 carbon atoms.
 3. The catalyst of claim 1 wherein saidcompound is a complex of the formula (MgR₂)_(m) (AlR₃ ')_(n) where R andR' are the same or different alkyl groups each containing from 2 to 10carbon atoms and m/n is between about 0.5 and
 10. 4. The catalyst ofclaim 1 wherein said alcohol comprises AOH in which A is an alkyl of1-10 carbon atoms.
 5. A dry, granular and solid olefin polymerizationand copolymerization catalyst active in a particle form process in thepresence of an alkyl aluminum cocatalyst, prepared by the consecutivesteps of:(a) preactivating and drying particles of an inorganic oxidehaving active surface hydroxyl or oxide groups chosen from the groupconsisting of silica, alumina and silica-alumina by heating saidparticles at between about 200° C. and 900° C.; (b) reacting said dryparticles in the presence of a hydrocarbon solvent with an alcoholcontaining only carbon, hydrogen and oxygen atoms and no aromatic ringbonded directly to the alcohol hydroxyl group and an organomagnesiumcompound comprising a magnesium alkyl compound, or a complex of thegeneral formula (MgR₂)_(m) (AlR₃ ')_(n) wherein R and R' are the same ordifferent alkyl groups of 2 to 10 carbon atoms and m/n is between about0.5 and 10, inclusive, to form a reaction mixture of said solvent and afirst reaction product insoluble in said solvent, the molar ratio ofsaid alcohol to said organomagnesium compound being 0.1-10; (c) reactingsaid first reaction product in said reaction mixture with ahalogen-containing transition metal compound to form a second reactionproduct, said transition metal compound being selected from the groupconsisting of Tr(OR")_(a) X_(4-a) and TrOX₃, wherein TR is a transitionmetal selected from the group consisting of titanium, vanadium, andzirconium, R" is an alkyl group of less than about 20 carbon atoms, X isa halogen atom, and a is zero or an integer less than 4; and (d)removing said solvent from said second reaction product to form saiddry, granular and solid catalyst.
 6. The catalyst of claim 5 whereinsaid compound is a magnesium alkyl of the formula MgR₂ where R is analkyl group of 2 to 10 carbon atoms.
 7. The catalyst of claim 5 whereinsaid compound is a complex of the formula (MgR₂)_(m) (AlR₃ ')_(n) whereR and R' are the same or different alkyl groups each containing from 2to 10 carbon atoms and m/n is between about 0.5 and
 10. 8. The catalystof claim 5 wherein said alcohol comprises AOH in which A is an alkyl of1-10 carbon atoms.
 9. The catalyst of claim 5 wherein between about 0.6and 2.5 mmoles of said transition metal compound is present per gram ofsaid inorganic oxide.
 10. The catalyst of claim 9 wherein between about0.25 and 1.0 mmoles of said transition metal compound is present permmole of said active hydroxyl and oxide groups on said inorganic oxide.11. The catalyst of claim 9 wherein said transition metal compound isadded in equimolar ratio to the total magnesium present in said firstreaction product.
 12. The catalyst of claim 5 wherein m/n is betweenabout 2 and
 10. 13. The catalyst of claim 5 wherein said inorganic oxideparticles are preactivated by heating at about 600° C.
 14. The catalystof claim 5 wherein said transition metal compound is chosen from thegroup consisting of TiCl₄, Ti(OR")Cl₃, Ti(OR")₂ Cl₂, Ti(R")₃ Cl, VOCl₃,VCl₄ and ZrCl₄.
 15. The catalyst of claim 5 wherein R" has between 2 and12 carbon atoms.
 16. The catalyst of claim 15 wherein R is butyl, R' isethyl, and m/n is about 6·5.
 17. The catalyst of claim 16 wherein saidtransition metal compound is TiCl₄.
 18. The method of preparing a dry,granular and solid olefin polymerization and copolymerization catalystactive in a particle form process in the presence of an alkyl aluminumcocatalyst comprising the consecutive steps of:(a) preactivating anddrying particles of an inorganic oxide having active surface hydroxyl oroxide groups chosen from the group consisting of silica, alumina andsilica-alumina by heating said particles at between about 200° C. and900° C.; (b) reacting said dry particles in the presence of ahydrocarbon solvent with an alcohol containing only carbon, hydrogen andoxygen atoms and no aromtaic ring bonded directly to the alcoholhydroxyl group and an organomagnesium compound comprising a magnesiumalkyl compound, or a complex of the general formula (MgR₂)_(m) (AlR₃')_(n) wherein R and R' are the same or different alkyl groups of 2 to10 carbon atoms and m/n is between about 0.5 and 10, inclusive, to forma reaction mixture of said solvent and a first reaction productinsoluble in said solvent, the molar ratio of said alcohol to saidorganomagnesium compound being 0.1-10; (c) reacting said first reactionproduct in said reaction mixture with a halogen-containing transitionmetal compound to form a second reaction product, said transition metalcompound being selected from the group consisting of Tr(OR")_(a) X_(4-a)and TrOX₃, wherein Tr is a transition metal selected from the groupconsisting of titanium, vanadium and zirconium, R" is an alkyl group ofless than about 20 carbon atoms, X is a halogen atom, and a is zero oran integer less than 4; and (d) removing said solvent from said secondreaction product to form said dry, granular and solid catalyst.
 19. Themethod of claim 18 wherein said compound is a magnesium alkyl of theformula MgR₂ where R is an alkyl group of 2 to 10 carbon atoms.
 20. Themethod of claim 18 wherein said compound is a complex of the formula(MgR₂)_(m) (AlR₃ ')_(n) where R and R' are the same or different alkylgroups each containing from 2 to 10 carbon atoms and m/n is betweenabout 0.5 and
 10. 21. The method of claim 18 wherein said alcoholcomprises AOH in which A is an alkyl of 1-10 carbon atoms.
 22. Themethod of claim 18 wherein between about 0.6 and 2.5 mmoles of saidtransition metal compound is present per gram of said inorganic oxide.23. The method of claim 22 wherein between about 0.25 and 1.0 mmoles ofsaid transition metal compound is present per mmole of said activehydroxyl and oxide groups on said inorganic oxide.
 24. The method ofclaim 22 wherein said transition metal compound is added in equimolarratio to the magnesium present in said first reaction product.
 25. Themethod of claim 18 wherein m/n is between about 2 and
 10. 26. The methodof claim 18 wherein said inorganic oxide particles are preactivated byheating at about 600° C.
 27. The method of claim 18 wherein saidtransition metal compound is chosen from the group consisting of TiCl₄,Ti(OR")Cl₃, Ti(OR")₂ Cl₂, Ti(OR")₃ Cl, VOCl₃, VCl₄ and ZrCl₄.
 28. Themethod of claim 18 wherein R" has between 2 and 12 carbon atoms.
 29. Themethod of claim 28 wherein R is butyl, R' is ethyl, and m/n is about6·5.
 30. The method of claim 29 wherein said transition metal compoundis TiCl₄.